Unraveling the Origin of Sulfur‐Doped Fe‐N‐C Single‐Atom Catalyst for Enhanced Oxygen Reduction Activity: Effect of Iron Spin‐State Tuning

Heteroatom doped atomically dispersed Fe₁ -NC catalysts have been found to show excellent activity toward oxygen reduction reaction (ORR). However, the origin of the enhanced activity is still controversial because the structure-function relationship governing the enhancement remains elusive. Herein, sulfur(S)-doped Fe₁ -NC catalyst was obtained as a model, which displays a superior activity for ORR towards the traditional Fe-NC materials. ⁵⁷ Fe Mössbauer spectroscopy and electron paramagnetic resonance spectroscopy revealed that incorporation of S in the second coordination sphere of Fe₁ -NC can induce the transition of spin polarization configuration. Operando ⁵⁷ Fe Mössbauer spectra definitively identified the low spin single-Fe³⁺ -atom of C-FeN₄ -S moiety as the active site for ORR. Moreover, DFT calculations unveiled that lower spin state of the Fe center after the S doping promotes OH* desorption process. This work elucidates the underlying mechanisms towards S doping for enhancing ORR activity, and paves a way to investigate the function of broader heteroatom doped Fe₁ -NC catalysts to offer a general guideline for spin-state-determined ORR.